MXPA98009956A - Composition of liquid detergent with peroxide, alcal - Google Patents

Abstract

Use of a salt of perborate or alkali metal percarbonate, as a buffering additive in the manufacture of a liquid detergent composition containing peroxide, alkaline, characterized in that the level of persalt added, based on the content of the peroxide, is less than 90 %, preferably less than 75%, more preferably less than half the total peroxide equivalent in the composition. Also a method for cleaning soiled laundry comprising the direct application to the laundry or a selected part of the laundry of a composition according to any of claims 5 to 8, optionally followed by a scrubbing action

Description

COMPOSITION OF LIQUID DETERGENT WITH PEROXIDE. ALKALINE DESCRIPTION OF THE INVENTION This invention relates to liquid detergent compositions with peroxides, alkaline, for washing fabrics. To obtain effective detergency from a liquid, alkaline detergent composition between a range of conditions of use, it is necessary that it be damped. Borax and sesquicarbonate and liquid detergent formulations are frequently incorporated. Both help maintain a high pH of the wash liquor. It is found in the present that each of these materials is incompatible with hydrogen peroxide. The sesquicarbonates give the required quenching, but they also give rise to a rapid decomposition of the peroxide. Borax gives lower but still unacceptable high levels of peroxide decomposition. Many publications mention the possibility of adding a persal such as perborate or percarbonate to an alkaline liquid detergent. It is usually suggested as a replacement for hydrogen peroxide which is the preferred form of peroxide. If it is desired to use in this form, then solid persalt may be present in the composition. Such use is described in EP-A-294 describing the formation of suspended sodium perborate crystals by recrystallization. There is a minor amount of hydrogen peroxide and salt dissolved in equilibrium with the recrystallized perborat maintained in the suspension. The reference teaches that this should be minimized by the use of a water miscible organic solvent to reduce the solubility of perborate in the liquid phase. WO 93/13012 discloses general purpose alkaline disinfectant or bleach compositions comprising less than 1% optional amine oxide surfactant, 0.5% borax and 5 or 10% hydrogen peroxide. The pH of the formulations tested with sodium hydroxide is adjusted to the relatively low initial value of 8.5 and the stability data at 12 weeks for the formulation with 5% hydrogen peroxide without any surfactant stored at approximately 30 ° C shows a loss low peroxide, but it is clear that the damping is not adequate as the pH decreases. There is no suggestion to use any other disodium tetraborate decahydrate (borax) as the buffer. WO 93/01270 discloses an alkaline aqueous liquid washing agent comprising surfactant, hydrogen peroxide and a water-soluble borate chosen from borax and sodium borate, the molar ratio of the peroxide: borate which is greater than 1.5: 1 and the composition which has an initial pH of less than 8 in all the examples. The invention resides in the ability of water-soluble borate and other ingredients to give an increase in pH to about 9 when the composition is diluted. All formulations contain solvents such as ethanol and propylene glycol. Sodium perborate is not used. There is no description or suggestion in the prior art that a quantity of persalt solution can be used to dampen a concentrated liquid with a pH d greater than 8.5 which contains hydrogen peroxide in solution. According to the present invention there is provided the use of an alkali metal perborate or percarbonate salt as a buffering additive in the manufacture of an alkaline liquid detergent composition containing peroxide with a pH of more than 8.5, characterized in that the level of the added persalt, based on the peroxide equivalent content is less than 90%, preferably less than 75% and more preferably less than half the peroxide equivalent of the composition. Preferably, the buffering agent is dissolved in the liquid detergent composition since it avoids the problem of suspending a solid component. This is especially advantageous if the composition is isotropic. The best combination of damping and peroxide stability is obtained when the damping additive is perborate, preferably, sodium perborate tetrahydrate or monohydrate. According to a second aspect of the present invention, there is provided a liquid alkaline peroxide detergent composition with a pH of more than 8.5, comprising surfactant, peroxygen bleach and soluble buffer, characterized in that the peroxygen bleach is hydrogen peroxide and the buffer is an inorganic persalt selected from alkali metal salts or alkaline earths of perborate and percarbonate, wherein the available oxygen of hydrogen peroxide exceeds that of the persalt, preferably at least 2: 1 and more preferably at least 3: 1. tf 10 Surfactants The compositions of the present invention comprise 5-60% by weight of surfactants. The peroxide reacts with many surfactants to give reaction products which cause a decrease in the pH of the composition. Using the buffers of the present invention may be used for a wide range of surfactants, which may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric surfactants and mixtures thereof. For example, they can be chosen from any of the classes, subclasses and specific materials described in "Surface Active Agents "Vol. Y, by Schwartz &Perry, Interscience 1949 and" Surface Active Agents "Vol. II by Schwartz, Perry &Berch (Interscience 1958); or in "McCutcheon 's Emulsifiers & Detergents "published by McCutcheon Division of Manufacturing Confectioners Company or in Tensid-Taschenbuch ", H. Stache, 2nd Edn., Cari Hanser Verlag, Munchen &Wien, 1981. Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide Specific nonionic detergent compounds are primary linear or branched alcohols or secondary alkyl (Cs.18) with ethylene oxide, * r 10 and products made by the condensation of ethylene with the reaction products of propylene oxide and ethylene diamine Other so-called non-ionic detergent compounds include amine oxides large chain tertiary, large chain tertiary phosphine oxides and dialkylsulphoxides 15 It is also possible to use active materials resistant to s altered such as described in EP 328 177, ^ g? especially the use of alkyl polyglycoside surfactants, such as described in EP 70 074. Suitable anionic surfactants are usually water-soluble alkali metal salts of organic sulfates and sulphonates having alkyl radicals containing from about 8 to about 22 atoms carbon, the term alkyl used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergents are sodium and potassium sulfates, especially those obtained from sulfonand higher alcohols (C8.18) produced for example from coconut oil or bait, sodium and potassium alkylbenzenesulfonates (Cg.20), particularly alkylbenzene sulfonates ( C10.1S) Secondary linear sodium; sodium alkyl glyceryl ether sulfates, especially those ethers of higher alcohols derived from coconut oil or bait and synthetic alcohols derived from petroleum; fatty monoglyceride sulfates of sodium coconut oil and sulfonates; sodium and potassium salts of sulfuric acid esters of higher fatty alcohols (C8.18), particularly ethylene oxide, reaction products; reaction producer of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of melataurine; alkane monosulfates such as those derived by reacting alpha olefins (C8_2p) with sodium bisulfite and those paraffin derivatives reactive with S02 and Cl2 and then hydrolyzing with a base to produce a random sulfonate; and olefin sulfonates, which are used in term to describe the material made, reacting olefins, particularly C10_20 alf-olefins, with S03 and then neutralizing and hydrolyzing the reaction product. Preferred anionic detergent compounds are sodium alkylbenzene sulphonates (C11-15) and amino acid derivatives, such as oleiolo sarcosinates can also be used. It is also possible to include an alkaline metal soap of a fatty acid, especially a soap of an acid having 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid and fatty acids derived from castor oil, alkylsuccinic acid, rapeseed oil, nutmeg oil, coconut oil, kernel palm oil or its mixtures. The sodium or potassium soaps of these acids can be used. Active material, total detergent from 0.5% to 60% by weight of the total composition, for example, from 1% to 40% and typically from 2% to 20% by weight may be present. However, a preferred class of compositions comprises 3-12% of the active detergent material based on the weight of the total composition. The actual amount of the surfactant used will depend on the application, the hard surface cleaner will have a low amount, a fabric pre-treatment composition, a different higher amount and a concentrated detergent at a high amount. Optional Ingredients The compositions of the invention may be isotropic (non-structures) or structures. The structured liquids of the invention can be internally structured where the structure is formed by the detergent active materials in the composition or externally structured. The compositions of the invention are preferably isotropic. The viscosity can be regulated by the use of one or more hydrothopes. It is preferred to avoid the use of 1,2 diols. The compositions of the invention may also comprise materials the pH. To lower the pH it is preferred to use weak acids, especially organic acids, more preferred is the use of carboxylic acids of C, __ B, the preferred carboxylic acid is citric acid. The use of these pH decreasing agents is especially preferred when the compositions of the invention contain enzymes such as amylase, proteases and lipolases. To raise the pH it is preferred to use sodium hydroxide, preferably pre-sequestered. Apart from the aforementioned ingredients, a number of other optional ingredients may also be present at levels below 5%, for example, skin reinforcers such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids, and acids coconut fatty acids, fabric softeners such as clays, amines and amine oxides, skin dispersants, regulators, inorganic salts, and usually present in very small, opaque quantities, fluorescent optical brighteners, perfumes, germicides, dyes and enzymes and enzymatic stabilizing agents. Other additives that can be incorporated are soil release agents such as Carboxymethylcellulose, also known as anti redeposition agents.; dye-transfer inhibiting polymers, ales such as polyvinylpyrrolidone and optical brightening additive (OBA) such as d-styrylbiphenyl derivatives. The compositions of the invention preferably comprise 10-93% by weight of water, more preferably 15-90%, more preferably 40-88%. The compositions of the present invention may comprise one or more bleach precursor agents. A well-known example of such an agent is TAED. Preferably, the bleach precursor agent is present in the system in at least partially the undissolved form. In use the detergent compositions of the invention will be diluted with wash water to form a wash liquor for example for use in a washing machine. The concentration of the liquid detergent composition in the wash liquor is preferably 0.05 to 10%, more preferably 0.1 to 3% by weight. The compositions can also be applied in pure form to clothing with soil as a pre-treatment. The damping makes them particularly beneficial for use as they retain alkalinity in storage and use and have a superior detergency against oil stains than an undamped or acidic liquid. SLi surface cleaners and general purpose cleaners are also used in pure form; but they can be diluted if required. Enhancers The present compositions may contain or reinforce, preferably at a level of not more than 50%, more preferably at a level of 5% to 40% of the total composition. If present, such reinforcers may consist of inorganic or organic types, organic enhancers are preferred. The liquid detergent compositions herein may optionally contain, as a reinforcer, a fatty acid component. Preferably, however, the amount of the fatty acid is less than 10% by weight of the composition, more preferably less than 4%. Preferred saturated fatty acids have from 10 to 16, more preferably 12 to 14 carbon atoms. The preferred unsaturated fatty acids are oleic acid and palmitoleic acid. Examples of organic reinforcers are polyacids, such as citric acids, nitrilotriacetic acid and a mixture of tartrate monosuccinate with tartrate disuccinate. Preferred builders for use herein are citric acid and alkyl (en) y-1-substituted succinic acid compounds C10.16. An example of this group of compounds is dodecenyl succinic acid. Polymeric carboxylagen boosters such as polyacrylates, polyhydroxyacrylates, polyacrylate copolymers / polymaleate may also be used. Sequents The compositions herein may also contain other components and / or additives at a level preferably less than about 5%. Non-limiting examples of such additives, which may be used more preferably at levels of 0.03% to 2% include polyaminocarboxylate additives such as ethylenediaminetetraacetic acid, diethylenetriamine pentacetic acid, ethylenediamine disuccinic acid or the water soluble alkali metals thereof. Other useful additives in these levels include organophosphonic acids; particularly preferred are ethylene diamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, aminotrimethylene phosphonic acid, and hydroxyethylidene diphosphonic acid. "Bleach stabilizers such as dipicolinic acid, sodium and 8-hydroxyquinoline statins may also be included in these compositions, preferably levels between 0.01 to 1%." Particularly preferred compositions of sequestrants are described in PCT / GB95 / 01537 and comprise diethylene diamine penta (methylene phosphonate) sodium as sold by Dequest 2066 by Monsanto (and hereinafter referred to as D2066) and 2, 2 '-dipyridylamin (referred to herein as DPA) and D2066 and 1,2-diaminocyclohexyl tetra (methylene phosphonic acid) and salts thereof (hereinafter referred to as DACH). The combination of sequestering agents gives universal sequestering performance in the transition metal ions. In general, these can be separated into two groups, Group A and Group B. The Group A sequestering agent preferably comprises one or a mixture of more than one of the sequestering agents, which is effective to stabilize the peroxide against decomposition by cobalt II ions under alkaline conditions. They can also be effective in sequestering the other transition metal ions. The Group B sequestering agent or a mixture of more than one sequestering agent which is effective to stabilize the peroxide against iron, copper or manganese under alkaline conditions, but substantially ineffective in stabilizing the peroxide against cobalt decomposition. The Group A sequestering agent is preferably selected from compounds having nitrogen donors as ligands, such as triazacycloalkane compounds especially 1,4,7-triazacyclononanes (TACN), or DPA, as well as some phosphonate compounds wherein the The molecule has limited flexibility and proper spacing of ligands such as DACH. DACH and / DPA are particularly preferred. The group B sequestering agent is preferably a non-cyclic alkylene amino poly (methylene phosphonic acid) or other phosphonic acid compound or salt thereof, especially the following agents under the Dequest brand: such as Deques 2006 sodium salt of (aminotris (methylene phosphonic acid )) ethylenediamine tetra (methylene phosphonic acid) or potassium sodium salt (for example, Dequest 2046 which is the sodium salt) diethylenetriaminepenta (methylene phosphonic acid) (Dequest 2060) 1-hydroxyethane-1,1-diphosphonic acid such as Dequest 2010 analogues with high alkylidene groups. D2060 and its sodium salt D2066 are particularly preferred. Other useful sequestering agents of group B are those sold under the trademark Briquest by Albright and Wilson. Compositions preferably free of ethanol, more preferably free of all volatile monohydric alcohols (ie having a point of combustion approximately equal to or less than isopropyl alcohol). The concentrated composition is alkaline. Preferably, the composition will have an initial pH of at least 9, preferably 9 to 11, and more preferably 9.5 to 10. The p of the composition after 6 weeks of storage at, 37 ° is preferably still greater than 9 and after 12 weeks of storage is still greater than 8.5.

The amount of the sequestering agent of group B a is incorporated in the oxidant composition of the invention is at least 0.005% by weight, preferably at least 0.01 by weight. Generally, it will not be greater than 2% by weight preferably not greater than 1% by weight, and more preferably not greater than 0.5% by weight of the total composition. The amount of the sequestering agent of group G a is incorporated into the oxidant composition of the invention is at least 0.005% by weight, preferably at least 0.01 by weight, preferably not more than 2% by weight or not greater than 1% by weight, or more particularly from 0.02 to 0.6% by weight. Optional additional sequestering agents may also be incorporated into the oxidizing composition. Where present, such additional optional sequestering agents are added in amounts of at least 0.005% by weight, preferably no greater than 2% by weight, more particularly in the range of 0.01% to 1.0%, more preferably in the range from 0.0 to 0.6% by weight. The invention will now be described with reference to the following non-limiting examples. Examples 1-2 and Comparative Example A The test formulations are prepared using 0.3% sodium percarbonate (Example 1) and 0.5% sodium perborate tetrahydrate (Example 2). It is compared against a control without buffer and comparative example A contains 4% sesquicarbonate. Table 1 shows the results. Sodium percarbonate does not give such effective peroxide retention as sodium perborate. Nevertheless, the percarbonate buffer system can be used either alone or in mixtures with perborate for detergents, short life requirement. The sesquicarbonate gives good damping, but the loss of peroxide is unacceptable. Further experiments show that borax gives good buffering which is marginally bad to those of Examples 1 and 2, but the loss of peroxide is much worse. Table 1 Examples 3 and, 4 Chlorine is added to maintain water disinfection. Sometimes the chlorine level is so high that it can get to the fabric dye damage, when you repeatedly wash your clothes with it. The use of low peroxide levels in a liquid detergent formulation should cause a reaction with chlorine which will reduce bleaching by chlorine. The peroxide also provides an increased bleaching in solution to give a reduced damage of the dye transfer during washing. Such a "color safety" formulation requires the use of a buffer for storage pH stability if it is to administer satisfactory removal of greasy soil in the wash. The liquid color security compositions are prepared which contain as a surfactant a 10: 2 ratio of a primary alcohol ethoxylated (C13_15), ethoxylated with 7 moles of ethylene oxide: linear alkylbenzenesulfonic acid (C10.13); giving a total of 12% of assets. The composition also includes 2% sodium citrate w / w as a booster, blue dye 80% acid 0.02% w / w as Tinopal CBS-X dye or distilledbiphenyl derivative ex Ciba Geigy, as an optical brightening agent. All the compositions have a sequestering system. Control 1 and Example 4 are sequestered with only 0.1% Dequest 2066 and Control 2, Examples 3A and 3B are sequestered with 0.1% Dequest 2066 and 0.03% DPA. The pH of the liquids is adjusted to 10 using 50% 50% w / w sodium hydroxide (containing 0.5% w / w Dequest 2066). S add the peroxide either as a 60% w / w H202 solution alone (and the controls) or with 0.5% sodium perborate tetrahydrate as a buffer, to give 1% w / w total equivalents of hydrogen peroxide in the controls and samples. The order of addition of the components is perborate, after peroxide solution, then sodium hydroxide. The composition of the examples is as follows: Control 1 -1% H202 (non-buffer) Control 1 -1% H202 (non-buffer) Examples 3A and 3B -0.85% H202 + 0.5% sodium perborate buffer p / p Example 4 -0.85% H202 + buffer 0.5% sodium perborate w / w Examples 3A and 3B are prepared as duplicates to check the reproducibility of the damped system. The reproducible stability is a key requirement for a commercial system. Many of the systems of the art are capable of giving good stability in a fixed base, but the effect is not reproducible. The formulations are stored at 25 and 37 ° C and the pH and oxygen available periodically are measured. The results are given in Table 2. Table 2 The buffering is significantly improved in duplicate Examples 3a and 3B containing 0.5% w / w of sodium perborate tetrahydrate in solution as a buffer. All examples show similar peroxide stability after 4 weeks of storage at 37 ° C. S knows that the peroxide is inherently more stable when the pH is lower. The stability of the two examples containing sodium perborate tetrahydrate is reproducible especially for large test periods. The beneficial effect of using l soluble persalt in a buffer is obtained for both sequestering systems. The broad utility of the invention is further illustrated by the following compositions, which can be formulated using the buffer system, which forms the subject of the invention. Example 5 Kitchen Spray Cleaner Water Deionized To 100 Hydrogen Peroxide (as 100%) 3.00 PBS4 0.50 Dequest 2066 0.25 DPA 0.02 Sodium Hydroxide At pH 9.5 Synperonic A7 2.50 * Proglyde DMM 3.00 * Gipropylene glycol dimethyl ether Example 6 Hard Surface Cleaner% Water Deionized To 100 Hydrogen Peroxide (as 100%) 4.30 PBS4 1.00 Synperonic A7 3.00 DPA 0.03 Dequest 2066 0.25 Sodium Hydroxide Up to pH 9.5 Example 7 General Purpose Cleaner Deionized Water Up to 100 Hydrogen Peroxide (as 100%) 3.70 Citrus Acid 3.00 PBS4 3.00 Dequest 2066 0.25 DPA 0.02 Sodium Hydroxide Up to pH 9.50 Synperonic A7 - 7.0 Example 8 Dual Compartment or Deionized Water Washing Liquid Up to 100 Alcano Sulfonate Secondary 8.00 Synperonic A7 2.00 Citrus Acid 3.00 Dequest 2066 0.50 DPA 0.03 Silicone Oil 0.10 Hydrogen Peroxide (as 100%) 3.50 Sodium Hydroxide at pH 9.50 PBS4 3.00

Claims (10)

1. The use of a salt of perborate or alkali metal percarbonate as a buffering additive in the manufacture of a liquid detergent composition which contains alkaline peroxide with a pH of more than 8.5 characterized in that the level of the persalt added on the basis of equivalent content of the peroxide is less than 90% preferably less than 75%, more preferably less than l half of the total peroxide equivalent of the composition.

2. The use according to claim 1 characterized in that the damping adhesive is substantially and completely dissolved in the liquid detergent composition.

3. The use according to claim 1, characterized in that the damping additive is a perborate sa.

4. The use according to claim 3, characterized in that the buffering additive is sodium perborat tetrahydrate or monohydrate.

5. An alkaline peroxide liquid detergent composition with a pH of more than 8.5 comprises surfactant, peroxygen bleach and a soluble buffer, characterized in that the peroxygen bleach is peroxide of hydrogen and the buffer is a selected inorganic persalt of alkaline salts of hydrogen peroxide. perborate and percarbonate, where the available oxygen of the hydrogen peroxide exceeds the persalt here preferably at least 2: 1, preferably at least 3: 1.

6. A composition according to claim 5, characterized in that they additionally comprise a sequestering system, preferably a combination of sequestrants, one that is from the sequestrant of group A and another a sequestrant of group B as defined herein.

The composition according to claim 5 or 6, characterized in that the inorganic persal is perborate tetrahydrate or sodium perborate monohydrate

8. An activated peroxygen bleaching system characterized in that it comprises a distribution container with two compartments, one of which contains a bleach activator and the other of which contains a composition according to claims 1 to 7.

9. A method for cleaning laundry, characterized in that it comprises the direct application to a selected part of the laundry of a composition according to any of claims 5 to 8, optionally followed by a scrubbing action.

10. The method for cleaning dirty soup according to claim 9, characterized by the direct application that is followed by washing the laundry in an automatic washing machine with the additional use of a laundry detergent conventional, optionally containing or activator of bleached such as tetraacetylethylenediamine.